Printing compositions and methods of printing therewith



Patented Dec. 5, 1944 UNITED STATES PATENT OFFICE PRINTING COMPOSITIONS AND METHODS OF PRINTING THEREWITH of Maine No Drawing. Application November 6, 1940, Serial No. 364,530

20 Claims.

This invention relates to compositions of developable colors suitable for printing by pianographic methods and methods of printing textiles and other fabrics therewith.

The standard method of printing textiles and other materials with developable colors, that is to say, colors which are applied to the fabric but which do not yield the final dye until they have been subjected to suitable chemical changes while on the textile, is by the so-called intaglio method. In this method the color or color elements and materials for. developing the color are made up into a rather thin printing paste which is transferred by a furnisher roll or other suitable means to depressions in a printing roll, such as for example a copper roll which has been etched in the design desired to be printed. The excess of printing paste is then removed from the surface of the rolls leaving paste only in the depression and the roll is then brought into contact with the fabric or other material to be printed. This is almost the only method which has been used successfully to print such developable colors as vat colors, hydrolyzable acid esters such as sulfuric esters of vat colors (the so-called indigosols), mixtures of stabilized diazo components and coupling components, and the like. The process has been used for many years on an enormous scale and where the print is not com posed of close fitting fine lines, and where the number of colors which are to appear in the print is not excessive, very satisfactory results may be obtained.

There are a number of instances in which, however, the intaglio method of printing a developable color is not satisfactory or is uneconomical. Patterns in which there are intricate close fitting thin lines of different colors require a plurality of printing operations because each color has to be applied by a separate roll. This requires a more elaborate machine and exact synchronization of the different color rolls, a procedure which is often difficult, and any lack of synchronization will result in a mis-matching of the print. Also, where the lines are very fine difficulty is encountered because intaglio printing requires a printing paste which is of rather moderate viscosity and is definitely fluid. I However these characteristics are largely incompatible with intricate patterns of adjacent or interweaving of fine lines because it is not not possible to provide a fluid paste which will leave the depressions of the roll efliciently and which will not also spread or run slightly. Not only are lines broadened out but,

where two lines of different colors appear close together, there is a tendency of one line to run intothe other. As a result, in the main, such intricate patterns have been avoided or considered impossible at present.

If a design is made up of a number of colors and printed by intaglio methods, one roll is required for each color. This increases very materially overhead because the copper rolls used represent a large capital investment. The printing of intricate designs having a large number of colors is, therefore, either very expensive or almost impossible to accomplish practically.

It has been found that the above disadvantages inherent in intaglio printing with developable colors can be avoided by using a planographic printing process in which the colors are present in the form of properly formulated solids or stiff putties which are transferred onto suitably wet ted fabrics. The use of such solid colors permits the printing of very fine lines, intricate patterns and designs in a great number of colors. There is no serious problem due to flowing or running. The finished solid color design contains all the colors to be applied thus making it possible to print practically any number of colors or shades simultaneously by a single impression.

In the past it had been considered that developable colors were completely unsuitable for printing by planographic methods and particularly developable colors in which all of the chemicals necessary for the afiixing to the fiber or development of the color were present in the printing composition. According to the present invention it has been found that by the use of suitable formulations it is possible to prepare putties of developable colors which can be used for pianographic printing. It should be realized plastic range with little tendency to stickiness,

yet they should fiow together readily under pressure so that blocks or other forms may be made employing a plurality of colors; (5) they should be sufliciently plastic, when soft, to permit forming thin sheets or fine threadlike lines.

Advantages of the present invention are: that the printing is not limited to designs having a relatively small number of shades and colors; that fine line patterns can be printed in different colors without diificulty; that both simple and intricate designs can be prepared easily by assembling and printing a small number of colored putties, in the case of the former, or a large number of colored putties in the case of the latter.

The colored blocks, putties, or magma of the present invention should not be confused with printing pastes as their properties are entirely different.

In general, the colored magma of the present invention require gums just as do printing pastes although here there is a rather sharp distinction. In printing pastes, the best results are ordinarily obtained by using high bodied gums such as certain white corn dextrines of the type of British gum. In the production of the colored magma of the present invention, while high-bodied gums may be used, the best results are obtained with the so-called highly degraded dextrines, examples being yellow corn dextrine, and the like.

Another factor which is desirable in the production of the colored magma by the present invention is the addition of soap. This is a feature which is avoided religiously in intaglio printing because soaps result in foaming and it is generally considered that a printing com position having soap incorporated therein, cannot be satisfactorily used for intaglio printing at all.

Another desirable feature is the addition of a wax or waxy substance. This is quite contrary to the customary practice in intaglio printing and while not essential to producing usable planographic printing blocks or forms according to the present invention, it is desirable for best results.

Wetting agents such as esters of sulfosuccinic acid and the like are also helpful in producing smooth uniform prints but are not essential.

The shapes into which the putties of the present invention are formed are in general different depending on the kind of printing and patterns which are to be effected. For discontinuous printing they will be in the form of discontinuous blocks. For printing the whole surface or coating they will be in the form of unbroken cylinders and the like. After the blocks have been placed in their supports they are then prepared in the way which is known to planographic printing art, that is to say, after molding into appropriate forms, cooling and hardening, the surface is machined and smoothed ready for use. Printing is then effected on a suitably prewetted or dampened fabric such as a textile fabric. Th wet cloth is brought in contact with the color block in a planographic printing machine in the usual manner and th color is transferred from the solid block to the fabric. From this point on, the fabric is handled in the same manner as is customary in intaglio printing. For example, a fabric after receiving an impression froma color block containin vat colors would be airdried, aged in a steam ager, and then oxidized in the usual manner, soaped, rinsed and dried. It is an advantage that except for the actual planographic printing, the procedure is not different from that used in intaglio printing. In other words, a printer who has equipment for intaglio printing requires only to substitute a planographic printing device for his intaglio printing device, and can use all the rest of his equipment as is.

Many printing establishments have a rather warm and moist atmosphere during part or all of the year. This sets up a problem of hygroscopicity and we have found that it is desirable to avoid the presence in any considerable amount of highly hygroscopic ingredients such as for example glycerine which has commonly been used in planographic printing blocks. The presence of hygroscopic material is not broadly excluded because it is of course possible to prepare putties of satisfactory physical characteristics according to the present invention which may contain considerable amounts of hygroscopic material. Such putties if printed promptly after opening the air-tight containers are fairly satisfactory but cannot be kept in a moist atmosphere. Therefore, in the preferred embodiment of the present invention we prefer to use putties which do not contain any considerable amount of highly hygroscopic material.

The invention will be described in conjunction with the following specific examples but it is not intended to limit the invention to the exact details therein set forth. The parts are by weight.

Example 1 4200 parts of British gum, 400 parts of tapioca flour and 1,000 parts of corn starch together with 5,000 parts of cold water are heated in a double boiler with constant stirring until about 2,000 parts of water are evaporated resulting in the formation of a fairly viscous paste. The paste is then allowed to cool, the stirring being maintained. 4,250 parts of the paste are then placed in a dough mixer, 1,000 parts of powdered sodium carbonate are added and the mixture is worked until it is of uniform texture. 1,600 parts of sodium formaldehyde sulfoxylate and 1,000 parts of colloidized vat pink powder of 6,6 dichloro-4,4-dimethyl bis thionaphthene indigo (colloidized by the procedure of the U. S. Patent Re. 21,402) are added in the above order each being intimately mixed before the next ingredient is incorporated. After all of the color has been thoroughly mixed in, a solution of parts of ferric chloride and 500 parts of water are added and the product dried under vacuum in an enameled tray at 65 C. After drying the product is ground in a Mikro mill using a screen. About 5,000 parts of the dry material are wet out with between 850-900 parts of distilled water in a steam jacketed stainless steel dough mixer and worked until a smooth homogeneous mixture is obtained. The mixing is continued, accompanied by spontaneous heating and the application of steam heat if necessary, with rapid loss of water. The temperature is held at 65-70 C. and from time to time a small sample is withdrawn, rolled between the fingers to form a small marble and placed on a flat surface. If the marble spreads under its own weight, the mixture is still too thin and the evaporation of water is continued until the marble shows no plastic deformation. The evaporation of water is then discontinued and the contents discharged into a shallow pan covered with Cellophane. On cooling, the product is very hard, softening when warmed in an air oven and can be readily cut with a knife. The material is formed into a suitable printing block, placed in a planographic printing machine and pigmented rayon wet out with approximately its own weight of water is printed therewith, sufficient pressure being applied to effect the transfer of the colored design. The printed rayon is then air dried, aged in a.

steam ager, oxidized, soaped and dried, resulting in a good strong pink print.

Example 2 The procedure of Example 1 is followed except that instead of using the dichloro dimethyl thionaphthene indigo, a corresponding amount of Vat Yellow GC (C. I. 1118) is substited and the ferric chloride is omitted. When printed on pigmented rayon a strong yellow print results.

Example 3 The procedure of Example 2 is followed to produce a blue powder, substituting Indanthrene Blue GCD (C. I. 1113) for the yellow color of Example 2. The product when placed in a planographic printing machine and printed on pig mented rayon gives a strong blue print.

The products of Examples 1, 2, and 3 are molded into a pattern of intricate design, placed in a planographic printing machine and printed on dyed pigmented French crepe which is finished as described in Example 1. Each of the colors gives good strong prints with remarkable details, showing colored discharges on a dyed ground.

Example 4 430 parts of a, 70% yellow corn dextrine slurry is heated in a double boiler with continual stirring until complete hydration has been effected giving a smooth uniform paste. Then 70 parts of an olive oil soap (28-30% moisture), 100 parts of technical sodium carbonate, 160 parts of sodium formaldehyde sulfoxylate and 100 parts of Scarlet 2GHN Double Powder or a mixture of Hydron pink and Hydron orange containing about 36 parts of real dye are added in the order given and worked in a dough mixer at '10-'75 C. When a marble of the hot material shows no gravity flow, the mixture is removed from the dough mixer, cooled, and when molded into a block and used in planographic printing, a smooth scarlet print on pigmented rayon or cotton is obtained.

Example 5 A thickener containing 21% B-2 British gum, 2% tapioca flour, and 5% corn starch on the finished weight of the gum is cooked in a double boiler until smooth and homogeneous. To this is added of sodium carbonate and 16% of sodium sulfoxylate formaldehyde. 1,000 parts of this printing thickener are worked on an ink mill with 100 parts of Jade Green NP Double Paste (C. I. 1101), containing about l2 real color at 60-65 C. Water is evaporated slowly, but continuously. The evaporation is continued until the hot product when made into a marble shows no appreciable gravity flow. This product gives excellent green prints by th planographic method.

Example 6 A prepared thickener containing 20% No. 1'77 dextrine, l sodium carbonate, l potassium carbonate, 7% sodium sulfoxylate formaldehyde, and 6% glycerine by weight is worked on an ink mill with an additional 27 parts of sodium sulfoxylate formaldehyde. 300 parts of the gum are used. Thirty parts of Vat Violet GRP Double (5,5'-dichloro-7,7 dimethyl 2,2 -bisthionaphthene indigo) Powder, prepared according to U. S. Patent Re. 21,402, are blended into the thickener and water is evaporated continuously until a, firm color solid is obtained. This product gives a good violet print on pigmented rayon when it is applied by the planographic method.

Example 7 1,024 parts of yellow dextrine are slurried with 350 parts of cold water in a steam-heated dough mixer. When the batch is well mixed, steam is turned on and the dextrine is cooked to a smooth, homogeneous paste. 320 parts of Jade Green NP Paste (C. I. 1101) are then added, 160 parts of olive oil soap, 40 parts of glyceryl mono-stearate, a waxy substance, and 20 parts of the isobutyl ester of sodium sulfosuccinic acid. The last three products are pasted in approximately parts of hot water to give a smooth plastic mass before they are added to the mixture. Otherwise, the addition is in the order given above. 200 parts of sodium carbonate and 440 parts of sodium sulfoxylate formaldehyde are then added. The sodium carbonate is dissolved in Water before adding. This miX is evaporated to the proper dryness under approximately fifteen inches of vacuum at 70-75 C. and gives a good solid product at the endpoint. Prints made therefrom on cotton, rayon, saponified cellulose acetate orsilk by the planographic method are smooth, bright and strong.

Example 8 800 parts of yellow dextrine are slurried with 450 parts of cold water and then cooked in a steam-heated vacuum dough mixer until a smooth homogeneous paste is obtained. 320 parts of colloidized Blue NTP Double Powder (chlorinated dibenzanthrone) containing 32% ,real dyestuff and prepared according to the U. S. Patent Re. 21,402 are added, mixed thoroughly and then parts olive oil soap, 40 parts glyceryl mono-stearate,and 100 parts of water are mixed and added. The last three products are pasted in an outside container as in the preceding example before being added to the dough mixer. 220 parts of sodium carbonate are dissolved in 550 parts of water and added to the mix, followed by 440 parts of sodium sulfoxylate formaldehyde powder. This mix is worked in the dough mixer and the water evaporates under partial vacuum of 20-24 inches, leaving the steam valve cracked during the evaporation. The product is dried until a piece chilled on an ice-cooled tin can be fractured when it is bent. The temperature is about 75-80" C. Prints made by the planographic method of this color give strong, bright color yields, showing excellent detail.

Example 9 800 parts of yellow dextrine are slurried cold in a steam-jacketed dough mixer with 1,135 parts of 6,6-dichloro-4A-dimcthyl-2,2-bis thionaphthene indigo dispersed press cake containing 320 parts of real color. Heat is applied and the mix cooked until uniform, then 160 parts of olive oil soap, 10 parts glyceryl mono-stearate, 240 parts of sodium carbonate, and 440 parts of sodium sulfoxylate formaldehyde are added. This mix is stirred in a steam-heated dough mixer with the steam valve cracked and water evaporates continuously until a thin disc of the material, when chilled on a fiat tin, will fracture when struck a blow with a hammer. The temperature reaches 75 C. during this experiment. Prints of this material made by the planographic process on pigmented rayon are strong, smooth and bright.

Example 10 A print thickener containing 2,100 parts of B-2 British gum, 200 parts of tapioca flour, 500 parts of corn starch, and 2,500 parts of water, are slurried cold until a smooth, uniform paste'is obtained, and then is heated in a steam-jacketed double boiler to a temperature of 185 F. This mixture is stirred and the heating is continued until the net weight of the material is 4,000 parts. 400 parts of this product and 100 parts of potassium carbonate are entered into a dough mixer and are worked until smooth. 160 parts of sodium sulfoxylate formaldehyde are added and the working continued until smooth. 100 parts of a colloidized double powder from a mixture of Hydron pink and Hydron orange containing about 36 parts real dye are then added, 3.3 parts of a 30% anthraquinone paste and 60 parts of glcyerine. The whole is worked until smooth and uniform which requires about 2 hours. It is then dried in a Monel metal pan in a vacuum oven at approximately 65 C. 300 parts of this product and 40 parts of distilled water are worked in a small dough mixer until a smooth, stiff, stringy dough is obtained that will not stick to the fingers. This product contains approximately 25% color, 12 potassium carbonate and 20% sulfoxylate.

Example 11 750 parts of the product prepared as in Example 9 and 150 parts of a 7% bentonite gel containing 1% sodium carbonate ar worked in a small dough mixer to which. heat is applied externally from a Bunsen burner. Water is evaporated until the same test is obtained as in Example 9. This product gives good smooth prints when applied planographically to rayon and cotton.

Example 12 1,600 parts of yellow dextrine and 500 parts of water are mixed cold in a steam-jacketed dough mixer to give a smooth paste. Steam then is admitted to the steam jacket and the dextrine paste is cooked. A dilute potassium carbonate solution (approximately is then added to the dextrine paste until a neutral reaction is obtained, as shown by testing with litmus paper. 180 parts of sodium bichromate are dissolved in water and ammonium hydroxide is added slowly to give a yellow chromate solution. 80 parts additional ammonium hydroxide are then added and the alkaline solution of sodium chromate I Example 13 1,000 parts of yellow dextrine are pasted with 550 parts of cold water in a small dough mixer. The mix is then cooked and made just alkaline. 160 parts of a mixed low titre soap, 40' parts of glyceryl mono-stearate, and 20 parts of isobutyl esters ofsodium sulfosuccinic acid are pasted in 100 parts of water in a separate container and then added to the dextrine mix. 200 parts of an equi-molar mixture of 2-methyl-5-chlorobenzene-diaZo-biguanide and the ortho toluide of 2-hydroxy-3-carboxy naphthalene, containing approximately parts of real color, 200 parts of butyl alcohol and 84 parts of 30 B. sodium hydroxide are slurried together then added to the mix. This is worked at fiv inches vacuum with the steam valve cracked to eliminate the excess water, and the working is continued until a thin section chilled on an ice cold tin fractures when struck a, blow with a blunt instrument. When this product is printed by the planographic process on cotton, and pigmented rayon, then acid aged, good strong prints are obtained.

Example 14 600 parts of 4H dextrine and 200 parts of cerelose are slurried cold in 400 parts of water, then cooked at 165 F. for fifteen minutes in a steam-jacketed dough mixer. 320 parts of Scarlet 2GHN powder or a mixture of Hydron Pink and Hydron Orange prepared according to U. S. Patent Re. 21,402 and containing approximately 115.2 parts of real color are added to the mixer. In a separate container, 160 parts of olive oil soap, 40 parts glyceryl mono-stearate and parts of water are stirred together, then added to the dyedextrine mix. 240 parts of sodium carbonate and 440 parts of sodium formaldehyde sulfoxylate are then added and stirring and evaporation of water continued until the cold product fractures when struck a blow with a blunt instrument. Prints of this product on cotton and rayon by the planographic method are smooth and strong.

The use of the term developable color in the claims is intended to cover only such colors which in the form in which they are present will not produce directly the final color on the fabric but which require further chemical reactions to develop the color or cause it to dye the fabric.

We claim:

1. A putty suitable for planographic printing comprising a developable color composition and a hydrophilic carbohydrate gum, the putty being characterized by hardness at room temperature, thermoplasticity and a long softening range the carbohydrate gum being the main bodying constituent.

2. A vat color'putty composition suitable for planographic printing comprisin a vat dyestufl, reducing agent, alkali, and a hydrophilic cartemperature, thermoplastic, and having a long softening range the carboyhdrate gum being the main bodying constituent.

3. A vat color putty composition suitable for planographic printing comprising a soluble ester of a vat dyestufi and a hydrophilic carbohydrate gum, the putty being hard at room temperature, thermoplastic, and having a long softening range the carbohydrate gum being the main bodying constituent.

4. A developable azo putty composition suitable for planographic printing comprising a diazo compound stabilized against azoic coupling in alkaline medium, a coupling component, and a hydrophilic carbohydrate gum, the putty being hard at room temperature, thermoplastic, and having a long softening range the carbohydrate gum being the main bodying constituent.

5. A vat color putty composition suitable for planographic printing comprising a vat dyestuff, reducing agent, alkali, a hydrophilic carbohydrate gum and a soap, the putty being hard at room temperature, thermoplastic, and having a long softening range the carbohydrate gum being the main bodying constituent.

6. A vat color putty composition suitable for planographic printing comprising a soluble ester of a vat dyestuff. a hydrophilic carbohydrate gum, and a soap, the putty being hard at room temperature, thermoplastic, and having a long softening range the carbohydrate gum being the main bodying constituent.

7. A developable azo color putty composition suitable for planographic printing comprising a diazo compound stabilized against azoic coupling in alkaline medium, a coupling component, a hydrophilic carbohydrate gum, and a soap, the putty being hard at room temperature. thermoplastic, and having a long softening range the carbohydrate gum being the main bodying constituent.

8. A vat color putty composition suitable for planographic printing comprising a vat dyestuff, reducing agent, alkali, hydrophilic carbohydrate gum, soap and a wax, the putty being hard at room temperature, thermoplastic, and having a long softening range the carbohydrate gum being the main bodying constituent.

9. A vat color putty composition suitable for planographic printing comprising a soluble ester of a vat dyestuff, a hydrophilic carbohydrate gum, a soap. and a wax, the putty being hard at room temperature, thermoplastic, and having a long softening range the carbohydrate gum being the main bodying constituent.

10. A developable azo color putty composition suitable for planograohic printing comprising a diazo compound stabilized against azoic couplin in alkaline medium. a coupling component. a hydrophilic carbohydrate gum, a soap and a wax, the putty being hard at room temperature. thermoplastic, and having a long softening range the carbohydrate gum being the main bodying constituent.

11. A vat color putty composition suitable for planographic printing comprising a vat dyestuif. reducing agent, alkali, hydrophilic carbohydrate gum, soap, and a mono-glyceride of a higher fatty acid, the putty being hard at room temperature, thermoplastic, and having a long softening range the carbohydrate gum being the main bodying constituent.

12. A vat color putty composition suitable for planographic printing comprising a soluble ester of a vat deystuif, a hydrophilic carbohydrate gum, a soap, and a mono-glyceride of a higher fatty acid, the putty being hard at room temperature, thermoplastic. and having a long softening range the carbohydrate gum being the main bodying constituent.

13. A developable azo color putty composition suitable for planographic printing comprising a diazo compound stabilized against azoic coupling in alkaline medium, a couplingcomponent, a hydrophilic carbohydrate gum and a monoglyceride of a higher fatty acid, the putty being hard at room temperature, thermoplastic, and having a long softening range the carbohydrate gum being the main bodying constituent.

14. A putty suitable for planographic printing comprising a developable color composition, a hydrophilic carbohydrate gum and bentonite gel, the putty being characterized by hardness at room temperature, thermoplasticity and a long softening range the carbohydrate gum being the main bodying constituent.

15. A vat color putty composition suitable for planographic printing comprising a vat dyestuff. reducing agent, alkali, bentonite gel and a hydrophilic carbohydrate gum, the putty being hard at room temperature, thermoplastic, and havin a long softening range the carbohydrate gum being the main bodying constituent.

16. A method of planographic printing which comprises subjecting a wetted fabric to contact with a printing block composed of a composit on comprising a developable color and a hydrophilic carbohydrate gum, the gum constituting the major bodying constituent and the printing block being hard at room temperature, thermoplastic and having long softening range.

17. A method of planographic printing which comprises subjecting a wetted fabric to contact with a printing block composed of a composition comprising a vat dyestuff, a reducin agent. an alkali, and a hydrophilic carbohydrate gum, the gum constituting the major bodying constituent and the printing block being hard at room temperature, thermoplastic and having long softening range.

18. A method of planographic printing which comprises subjecting a wetted fabric to contact with a printing block composed of a composition comprising a soluble ester of a vat dyestuff and a hydrophilic carbohydrate gum. the gum constituting the major bodying constituent and the printing block being hard at room temperature, thermoplastic and having long softening range.

19. A method of planographic printing which comprises subjecting a wetted fabric to contact with a printing block composed of a compos tion comprising a diazo compound stabilized against azoic coupling in alkaline medium, a coupling component and a hydrophilic carbohydrate gum, the gum constituting the major bodying constituent and the printing block being hard at room temperature, thermoplastic and having long softening range.

20. A method of planographic printing which comprises bringing a wetted fabric into contact with a printing block having a design in a plurality of colors, the block consisting of a putty comprising a developable color composition and a hydrophilic carbohydrate gum, the gum constituting the major bodying constituent and the printing block being hard at room temperature, thermoplastic and having long softening range.

ROY HERMAN KIENLE. CHESTER ALBERT AMICK. CLARENCE CLIFTON KERNS. 

